Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
  • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
  • C08F4/61908—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
  • C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
  • C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
  • C08F4/61922—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
  • C08F4/61927—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S526/943—Polymerization with metallocene catalysts

Definitions

• the invention further relates to a method for manufacturing such ethylene copolymers, the use of the ethylene copolymers for the production of foils, hollow bodies and fibers as well as foils, Hollow bodies and fibers made using these ethylene copolymers getting produced.
• opening angle between the cyclopentadienyl rings of the metallocene has a great influence on the installation behavior.
• a large opening angle can be achieved, for example, by bridging the rings through a SiMe 2 or C 2 H 4 bridge.
• Such metallocene catalysts are described, for example, in EP 336128.
• Methods for supporting metallocene catalysts are e.g. in WO 95/07939 WO 87/03889, WO 94/28034, EP 206794 and EP 250600 described.
• MAO methylalumoxane
• WO 94/28034 a other alumoxane used as cocatalyst.
• Methods for Support of metallocenes in which boron compounds as Activator have already been described (see e.g. WO 91/09882, WO 94/03506, WO 95/14044, EP 628574, WO 95/15815).
• the polymers made with these supported catalysts usually have a very narrow molecular weight distribution and at the same time a very even comonomer installation on what is in some desirable properties such as tear resistance and gloss of the films made from these materials results.
• the narrow molecular weight distribution becomes processing very difficult on machines customary in the polymer industry.
• Polymers with a broader molecular weight distribution as you can e.g. with the help of chromium or titanium catalysts can be processed much better, but have the disadvantage that the comonomer (e.g. butene, hexene, octene) unevenly on the Polymer molecules is distributed. So is in the low molecular weight fraction a significantly higher proportion of comonomers than in high molecular weight fraction. Therefore, these are easy to process Polymer weaknesses in the mechanical properties.
• EP-A-613908 describes the preparation of copolymers with a molecular weight distribution M w / M n of up to 32, but these copolymers also have a broad comonomer distribution.
• WO 93/09148 also describes copolymers with a wider range Molecular weight distribution described, this broadening goes but also at the expense of a broader comonomer distribution as well as a large, low molecular weight fraction, which is in one high hexane extractable content of 4.1 to 13.3%.
• the present invention was based on the object to find ethylene copolymers of units of ethylene and at least one C 3 to C 12 - ⁇ -olefin with a molecular weight distribution> 3, which nevertheless have a narrow comonomer distribution.
• the narrow comonomer distribution of the copolymers according to the invention can be described in an advantageous manner by means of the standard deviation of the mean weighted elution temperature T a , as can be determined by the TREF method.
• the TREF method is described, for example, in Wild, Advances in Polymer Science, 98, p. 1-47, 1990, Springer-Verlag and Wild, Blatz, Polymer Mater. Sci. Closely. 67 p. 153, 1992.
• the mean weighted elution temperature (T a ) and the standard deviation ( ⁇ ) are used as follows (see also Bevington, Mc Graw-Hill, Data Reduction and Error Analysis for the Physical Sciences, 1969).
• T a ⁇ (c (T i ) * T i ) / ⁇ c (T i ) [° C]
• ⁇ ([ ⁇ (T i -T a ) 2nd * c (Ti)] / ⁇ c (Ti)) 1/2 [° C]
• T i mean the temperature at point i and c (T i ) the polymer concentration at temperature T i
• the copolymers according to the invention now have an unusually low standard deviation ⁇ , which can be described by equation GI with the above-mentioned values for k o , k 1 , k 3 , and k 4 .
• the advantageous properties of the copolymers according to the invention are based essentially on the combination of this narrow comonomer distribution with a relatively broad molecular weight distribution.
• This molecular weight distribution M w / M n must assume a value> 3, preferably a value> 3 and ⁇ 8 and particularly preferably a value between 3.5 and 7.0.
• the copolymers according to the invention also contain those of at least one C 3 - to C 12 - ⁇ -olefin.
• Suitable ⁇ -olefins are propene, butene, pentene, hexene, heptene, octene, nonen, decene, undecene and dodecene.
• Comonomer units which are derived from butene and hexene are preferred.
• the proportion of comonomers in the copolymer depends on the desired density of the copolymer.
• the copolymers according to the invention usually contain a comonomer content which results in a density of 0.87 to 0.96 g / cm 3 , preferably 0.90 to 0.94 g / cm 3 , particularly preferably 0.910 to 0.935 g / cm 3 .
• the copolymers according to the invention can have very different molecular weights, it being possible for the setting of the desired molecular weight to be influenced by methods which are known to the person skilled in the art, for example by means of the polymerization temperature or by means of reagents such as hydrogen.
• the copolymers usually have a molecular weight M w > 100,000, preferably> 150,000.
• copolymers that have a small proportion of low molecular weight polymer chains. That share of also characterized by the proportion of the parts extractable with heptane has a negative impact e.g. on the organoleptics of the copolymers.
• the heptane extractable portion of the copolymers according to the invention is preferably less than 4% by weight, particularly preferably less than 1% by weight and in particular less than 0.1 wt .-%, based on the total mass of Copolymers.
• Finely divided solids are preferably used as carrier materials used, the particle diameter in the range of 1 to 200 microns lie, in particular 30 to 70 microns.
• Suitable carrier materials are, for example, silica gels, preferably those of the formula SiO 2 .a Al 2 O 3 , in which a stands for a number in the range from 0 to 2, preferably 0 to 0.5; So these are aluminosilicates or silicon dioxide. Products of this type are commercially available, for example silica gel 332 from Grace or ES 70x from Crosfield.
• carrier materials can be used to remove the adsorbed Water undergo a thermal treatment or else be calcined, preferably a treatment at 80-200 ° C. preferably at 100-150 ° C.
• inorganic compounds such as Al 2 O 3 or MgCl 2 or mixtures containing these compounds can also be used as carrier materials.
• M 1 is a metal of III.
• the main group of the periodic table is, in particular for aluminum, R 1 for C 1 to C 10 alkyl and R 2 to R 4 for C 1 to C 10 alkyl.
• u is zero and the radicals R 1 to R 3 have in particular the same meaning, preferably methyl, ethyl, isobutyl or hexyl, preferably isobutyl.
• the metal compound of the general formula I is preferably added as a solution to a suspension of the carrier.
• a solution or Suspension agents are in particular hydrocarbons such as Suitable for heptane.
• the amount of metal compound I can vary widely Limits vary, the minimum quantity depends on the number the hydroxyl groups of the carrier.
• the temperatures, reaction times and pressures are not critical per se, temperatures are preferred from 0 to 80 ° C and reaction times from 0.1 to 48 hours.
• the material produced in this way can be stored for at least 6 months and not pyrophoric.
• This material is now in a further stage B) with a Metallocene complex in its metal dihalide form and one Implemented metallocenium ion-forming compound.
• metallocene complexes of the general formula III are such preferred in which the bridged cyclopentadienyl ligands the indenyl, tetahydroindenyl or benzindenyl ring system deduce. Furthermore, such compounds III are preferred in which the substituted or unsubstituted cyclopentadienyl ligands with ethylene groups, substituted ethylene groups or are bridged with dimethylsilyl groups.
• Examples of particularly suitable complex compounds include Dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, Dimethylsilanediylbis (indenyl) zirconium dichloride, Dimethylsilanediylbis (tetrahydroindenyl) zirconium dichloride, Ethylene bis (cyclopentadienyl) zirconium dichloride, Ethylene bis (indenyl) zirconium dichloride, Ethylene bis (tetrahydroindenyl) zirconium dichloride, Tetramethylethylene-9-fluorenylcyclopentadienylzirconium dichloride, Dimethylsilanediylbis (3-tert.butyl-5-methylcyclopentadienyl) zirconium dichloride, Dimethylsilanediylbis (3-tert.butyl-5-ethylcyclopentadienyl) zir
• Suitable compounds which form metallocenium ions are in particular strong, neutral Lewis acids, ionic compounds with Lewis acid cations and ionic compounds with Bronsted acids as a cation.
• Carbonium cations, oxonium cations and Sulfonium cations and cationic transition metal complexes are carbonium cations, oxonium cations and Sulfonium cations and cationic transition metal complexes.
• Ionic compounds with Bronsted acids as cations and preferably also non-coordinating counterions are in WO 91/09882 called, preferred cation is the N, N-dimethylanilinium.
• the amount of compounds forming metallocenium ions is preferably 0.1 to 10 equivalents, based on the metallocene complex III.
• the conditions for the implementation of the metallocene complex with the metallocenium ion-forming compounds are not critical per se, it is preferred to work in solution, the solvent being in particular Hydrocarbons, preferably aromatic hydrocarbons such as toluene.
• a Amount of 0.1 to 10 wt .-% of metallocene complex, based on the inorganic carrier material is particularly suitable.
• the conditions temperatures are also not critical for this implementation in the range of 20 to 100 ° C and reaction times in the range of 0.1 to 20 hours have proven to be particularly suitable.
• the material obtained according to B) can now be isolated and is Can be stored for at least 6 months.
• the activation stage this is after B) material obtained with a metal compound of the general Formula II implemented.
• This activation can be any Time, d. H. before, at or after the dosing according to B) obtained material into the reactor. Preferably done activation after dosing the one obtained in B) materials in the reactor.
• stage C The conditions for the implementation in stage C) are not critical per se. Temperatures, reaction times and pressures depend on each other the time of implementation, i.e. Activation.
• the copolymerization process according to the invention can be carried out in Suspension or be carried out in the gas phase, the Gas phase polymerization is preferred.
• copolymers according to the invention are suitable because of their mechanical properties and their workability excellent for the production of foils. This is how these copolymers can be mostly on common devices, such as those like them for by Ziegler or Phillips catalysis or for by radical high pressure polymerisation are used for foils and also for hollow bodies and fibers to process.
• the films have excellent strength and very good optical properties.
• the TREF investigations were carried out under the following experimental conditions carried out: solvent: 1,2,4-trichlorobenzene, Flow: 1 ml / min, heating rate: 1 ° C / min, amount of polymer: 5-10 mg, carrier diatomaceous earth.
• the molecular weights of the copolymers were determined by GPC studies determined in accordance with DIN 55672 under the following conditions: Solvent: 1,2,4-trichlorobenzene, flow: 1 ml / min, Temperature: 140 ° C, calibration with PE standards.
• T a 90.78 ° C
• Example 8 ⁇ 3.92 ° C
• T a 89.01 ° C.

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• 1998
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